NTC Project: M00-MD08 (formerly M00-D08)

Nanocomposite Fibers
Project No: M00-MD08 (formerly M00-D08)
Investigators: Yong K. Kim (Leader), A. F. Lewis, S. B. Warner, P. K. Patra
P. D. Calvert
Graduate Students: Shamal K. Mhetre and Ceyhan Celik
ABSTRACT
During the last two years, studies on the creation of nanocomposite fibers has been approached from: (1) mixing of
nanoparticles in polymer solutions, (2) polymer melt blending (compounding) of nanoparticles into fiber forming
polymers, (3) in situ polymerization of monomer/nanoparticle mixtures as well as in situ formation of nanoparticle
entities in the polymer structure and (4) study on the use of ultrasonic methods to disperse nanoparticle (especially
carbon nanotubes - CNT) into individual particulate species. It was found that traditional polymer melt blending
techniques for the creation of CNT containing nylon and polybutyleneterephthalate (PBT) fiber producing polymers
were not successful. Poor particle dispersion and weak fibers result. Mixing of nanoparticles in polymer solutions
also resulted in improper dispersion when polymer solvent is evaporated after ultrasonication. However, promising
results were achieved using in-situ polymerization of Nylon 6 under the presence of Carbon Nanotubes and
sonication treatment before polymerization. Dispersion was found to be very good compared to previously prepared
fibers from melt blending CNTs in fiber grade nylon 66 and PBT polymer. Here some concentrates of 20%
carbon (multiwall) nanotubes in nylon 66 and polybutylene terephthalate (PBT) were used. Studies on electrical
properties of nanocomposites show that particle size and shape, mixing time, filler concentration, composite
processing technique, and filler/matrix interactions are significant factors, affecting the electrical resistance of CNT
nanocomposites.

OBJECTIVE
The objective of this research is to explore the structure, properties, and processing of fibers that contain nanoscale
embedded hard particles. The particles may be another polymer, ceramic, metal, carbon nanotubes, or graphite, but
they must be on the size scale of nanometers in dimension. Hence, a large portion of the composite fiber is
effectively interfacial material in which the two phases are intimately blended. This should provide the fibers with
unique structure and properties.

INTRODUCTION
Nanocomposites are a distinct form of composite materials, which involve imbedding nano or molecular domain
sized particles into organic polymer, metal or ceramic matrix materials. In all cases, it is perceived that the intimate
inclusion of these nanoparticles in these matrices can completely change the properties of these materials. The
nanoparticles can serve as matrix reinforcement as well as change the electrical behavior of these base materials.
The reason for this is that with such small inclusions, a large amount of interfacial phase material is now included in
the bulk of these nanocomposites. A complete transformation of the materials chemical, mechanical and
morphological domain structure can be achieved by the proper addition of nanoparticles.

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Much of todays research activity is in the field of organic polymer based nanocomposites. In all such work, the
technical challenge is the need to obtain intimate blending of these nanofibers and particles into the polymer
matrices. Two problems exist: (1) the need to blend and distribute individual nanofiber species into the bulk polymer
matrix and (2) induce chemical compatibility (adhesion) between the nanofibers and the polymer media. Most forms
of nanofibers are agglomerated entities. They exist as bundles of nanoparticles and are very difficult to separate and
keep separated. While some techniques have been reported for exfoliating and chemically surface modifying or
functionalizing of carbon nanotubes, none of these techniques have been entirely successful or particularly practical
[1][2]. Therefore getting a proper intimate blend of these molecular sized particles into a polymer matrix offers a
very difficult research challenge.
This NTC research project focuses on the creation of Nanocomposite Fibers. Here one must determine ways of
intimately blending individual entities of nanofibers, such as carbon nanotubes and SiC whiskers, silica and clay,
into polymers with the goal of producing new forms of textile fibers. The properties of these presumed fibers will be
widely different from the spectrum of fiber forming polymers that now exist. One might expect the modulus and
strength of existing fiber polymers to be greatly enhanced by the addition of nanofiber reinforcement. If carbon
nanotube (CNT) fibers were used, one would expect a great increase in the electrical conductivity of the soreinforced fibers since CNTs themselves are electrically conducting. Nanofiber particle reinforced fiber polymers
such as nylon, polyester, acrylic, cellulose etc. are important fiber composites to study as the more traditional choice
of fiber producing polymer. This present study has approached the problem of mixing the nanoparticle
reinforcement in the base polymer in several ways.
The following sets an outline of the research carried out during the past two years.
(1) Mixing nanoparticles into a solvent solution of the polymer and evaporating or coagulating off the solvent. This
process is similar to wet spinning.
(2) Rheological melt mixing of nanoparticles into base polymer; traditional polymer compounding.
(3) In situ formation of nanoparticles or the polymerization of monomers in the presence of nanoparticles.
(4) Disruption processes that will lead to the separation of agglomerated nanofibers or nanoparticles. These single
nanoparticles would then be mixed into polymer matrices to form nanocomposite fibers (as described above).
Approaches (1), (2) and (4) resulted in non-uniform dispersion of particles (carbon nanotubes) in the matrix. It is
observed that dispersed carbon nanotubes agglomerate again as solvent starts evaporating from polymer solution and
forms the clusters in the composites prepared. While it is found that, in melt mixing it is very difficult to separate
nanoparticles due to high viscosity of polymer melt. The excessive use of shear blending results in polymer
degradation. So in this year we are currently focusing on In situ polymerization of monomers in the presence of
nanoparticles. The preliminary experiments performed on this approach have resulted in some interesting results.
The uniformity of nanoparticles is found to be very good in the prepared nanocomposites. It was also noted that the
fibers formed, can be easily stretched and prepared fibers have good strength.
It is now known that properties of nanoparticles cannot be fully realized if there is poor interaction or adhesion
between nanoparticle and polymer matrix. We are also working on surface modification of carbon nanotubes by
carboxylic functionalization using acid treatments and non-covalent wrapping of polyvinyl pyrrolidone molecules
on carbon nanotubes. These functionalized carbon nanotubes will be finally used in in-situ polymerization and melt
mixing methods of creating nanocomposites. Functionalization can give stronger adhesion (matrix to carbon
nanotube) and mechanical interlocking between polymeric molecules and molecules attached to carbon nanotubes.
In nanocomposite preparation it can give additional advantages like easy solubility in solvents and good uniform
dispersion.
One of the objectives of this research is to achieve electrically conductive polymer nanocomposites at low particle
loading. The conductive fillers can be carbon black, graphite, carbon nanotubes and metal fillers. However, carbon
based filler shows advantages such as, lighter weight, resistance to corrosion, and the ability to be readily adapted to
the needs of a specific application, over metallic fillers. We use expanded natural flake graphite, supplied from
Asbury Carbons Inc.
In this study, we are investigating the parameters that affect the resistivity of the composites, such as particle size
and shape, mixing time on filler distribution, filler concentration, composite processing technique, and filler/matrix
interactions.

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EXPERIMENTAL MATERIALS AND METHODS
Materials and Sources of Nanoparticle Materials:
(1) Carbon Nanotubes (CNT) CarboLex AP, Carbolex Inc. Lexington, KY
(2) 20% Concentrate of multiwall CNTs in nylon 66 Fibril. Nylon 66, Hyperion Catalyst Inc. (HCI),
Cambridge, MA
(3) 15% Concentrate of multiwall CNTs in polybutylene terephthalate Fibril. (PBT) from HCI
(4) Graphite powder pristine graphite, Lubbock Gasket & Supply, Lubbock, TX
(5) Expanded and natural flake graphite, supplied from Asbury Carbons Inc., Asbury, NJ
Equipment and Services Used:
(1) Ultrasonic Disrupter - 750 Watt, Ultrasonic Processor (homogenizer), Cole-Palmer
(2) Twin Screw Extruder mixing and fiber preparation Polymer melt mixing and fiber preparation services
provided by Albany International, Mansfield, MA
(3) SEM Photographs JEOL Model 6510 (ATMC, UMD)
(4) Polarized light microscopy - Leica Model MPS 60, Leica USA, Deerfield, IL
(5) Brabender Plasticorder, CW brabender. (ATMC, UMD)

RESULTS AND DISCUSSION

1. In situ polymerization of monomers in the presence of nanoparticles.
(a) In situ polymerization of nylon 6 in the presence of carbon nanotubes
Monomer -caprolactam, polyoxyethylene (POE) (M. W. - 6000) and N- acetylcaprolactam (few drops) were first
melted in test-tube. After complete melting, 1% carbon nanotubes by weight of monomer were added to the melt
solution. The melt solution was then subjected to 1 minute of ultrasonication (80 % amplitude) to disrupt the carbon
nanotubes. Then a spatula tip of initiator sodium hydride (NaH), 60% dispersion in oil, was added to the melt
solution to carry out the polymerization.
In the resulting polymer nanocomposite the dispersion of carbon nanotubes was found to be very good compared to
previous experiments on melt mixing of carbon nanotubes in Nylon 6, 6. Figure 1 shows polarized microscope
image of nanocomposite fiber produced by melt mixing technique, while Figure 2 shows polarized microscope
images of nanocomposite fiber produced by in-situ polymerization technique.
Also the previous melt mixing experiment produced only low strength, unevenly dispersed and brittle filament
fibers. Figure 1 shows the carbon nanotubes in the produced CNT/ nylon 66 composite fiber exist as agglomerates.
These discontinuous particulate inclusions are localized in specific areas and lead to stress concentrations when the
fiber is under stress. This causes the fibers to be mechanically weak and brittle. But nanocomposite fibers produced
by in situ polymerization are found to be stretchable and having good strength. Stretching of fibers can also lead to
orientation of carbon nanotubes inside fibers, which can further increase strength

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Figure 1. Polarized Light Microscope Image of CNT/Nylon 66 (CNT 4%) Extruded Fiber by Melt Mixing.

Figure 2. Polarized Light Microscope Image of CNT/Nylon 6 (CNT 1%) Fiber prepared by In-situ Polymerization
Technique.
and modulus of fibers. We believe that following is the mechanism that contributes to a good dispersion of carbon
nanotube in fibers prepared by in-situ technique. Figure 3 and Figure 4 shows the chemical structure of monomer caprolactam and single wall carbon nanotube respectively.

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Figure 3. Monomer -caprolactam used in Nylon 6 Polymer.

Figure 4. Ring Structures in Carbon Nanotubes.

It is hypothesized that since carbon nanotube and monomer -caprolactam both have ring structures, -caprolactam
in molten form can be compatible with carbon nanotubes and can wet its structure. Ultrasonication can help to
efficient separation and dispersion of carbon nanotubes inside the polymer. Also the low viscosity of monomer
solution before polymerization (the stage where carbon nanotubes were added and solution was given
ultrasonication treatment) can be an important factor behind the wetting and efficient dispersion of the carbon
nanotubes. Once the polymerization is completed solution becomes very viscous so there is little possibility of reagglomeration of carbon nanotubes inside nylon 6 polymer.
A detail analysis of these nanocomposites using TEM (for microstructural image studies and dispersion studies) and
quantitative mechanical properties comparison with virgin Nylon 6 fibers is in progress.
2. Electrical properties of nanocomposites
(a) Graphite Embedded Nanocomposites
In this study, we are investigating the parameters that affect the resistivity of the composites, such as particle size
and shape, mixing time on filler distribution, filler concentration, composite processing technique, and filler/matrix
interactions. In order to observe the influence of particle size on the conductivity of the composite, we studied three
different grades of expanded graphite.
Table 1. Expanded Graphite grades used in the experiments.
Particle
Expanded Graphite
Expanded Graphite
Expanded Graphite

Mesh
140-325
60-140
40- 60

Micrometer
44-105
105-250
250-500

We use expanded natural flake graphite, supplied from Asbury Carbons Inc. Expanded Graphite (EG) is a material
of scientific and industrial interest. It is produced by exfoliation of graphite intercalation compounds. Graphite can
react with both oxidizers and reducers [3]. When they are going to be combined with polymers, expandable graphite
particles are usually mixed and saturated with oxidizers and the intercalants. A mixture of acids (concentrated
sulfuric acid and concentrated nitric acid) and graphite is the usual recipe for graphite intercalation compounds,
GICs [4]. The nitric acid serves as an oxidizer and the sulfuric acid serves as an intercalant [5]. The process,
through rapid heating of a GIC, induces vaporization and dislocation of the intercalated species. If the pressures of
the gasified intercalate increases excessively on heat treatment of GICs, a significant expansion along the c-axis
takes place as shown in Figure 5. Expansion of graphite results in many pores of different sizes ranging from 10 nm
to 10 micrometer. It has a loose vermicular structure and a very low density in the range of 3-10 kg/m3 [5, 6, 7].

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(a)
(b)
Figure 5. SEM Photomicrographs of (a) Natural Flake Graphite, (b) Expanded Graphite Showing Abundant
Multi-Pores.
The expanded graphite was melt blended with Noryl, a modified PPE/PS blend (General Electric Plastics), in a
Brabender mixer. The mixing was carried out at 275C, using a screw speed of 30 rpm for 10 minutes. The
specimens were prepared in a compression molding machine, and their surface resistivity was measured on 1cm2
area specimens using a Mahlo Control Systems, DMB-10 Textometer.
Table 2. Surface Resistivity of EG filled Noryl.
Graphite Size Range

Expanded Graphite Concentration

250-400m
Sample
Designation
105-250m

44-105m

10 wt%
5 wt%
2 wt%
1 wt%
10 wt%
5 wt%
1 wt%
10 wt%
5 wt%
1 wt%

Surface Resistance
()
1.0x104
4.2x109
7.8x1011
---*
8.2x107
---*
---*
9.1x108
---*
---*

* Resistance above 1012 could not be measured because of the limitations of the testing device.
The results show that, the surface resistance of EG filled samples at 10 % loading of expanded graphite decreases as
the particle size increases.
3. Functionalization of Carbon Nanotubes
(a) Carboxylic Functionalization Using Acid Treatments
This experiment consisted of treating raw, as prepared carbon nanotubes with concentrated nitric acid (HNO3) and
sulphuric acids. Figure 6 describes the reaction involved in this process

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OH

OH

H2SO4/HNO3

HO
O

HO

HO

O
HO

Figure 6. Chemical Reaction involved in Acid treatment of Carbon Nanotubes.

The reaction was carried out at elevated temperature 100-110 C with ultrasonication for 2 hours (80 % amplitude).
The resulting solution was diluted with water and then filtered using PVDF 0.1 um pore size filters. The treated
carbon nanotubes were washed several times with deionized water. This treatment simultaneously gives
purification, shortening and opening of raw carbon nanotubes.
The Figure 7 shows SEM picture of as received carbon nanotubes while Figure 8 shows SEM image of acid treated
carbon nanotubes. Breaking of agglomeration and shortening can be easily seen in these images.

Figure 7. As Received Raw Carbon Nanotubes.

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Figure 8. SEM Image of Acid Treated Carbon Nanotubes.

The Figure 9 shows FTIR analysis of functionalized carbon nanotubes, which indicates introduction of (OH) and (
C=O) bonds in the carbon nanotubes. These functionalized carbon nanotubes will be used in in-situ polymerization
(Nylon 6) and melt mixing methods of preparation of nanocomposites fibers.

Figure 9. FTIR Spectrum of Acid Treated Carbon Nanotubes. .

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CONCLUSIONS
The in situ polymerization to prepare nanocomposite fibers is a promising technique. Very good dispersion was
observed in nylon 6/carbon nanotube nanocomposite. It is felt that wetting of carbon nanotubes by the nylon 6
monomer mixture and the low viscosity of the reaction mixture at the time of ultrasonication contributes towards the
good dispersion of carbon nanotubes in the nanocomposite.
Functionalization of carbon nanotubes reduces the agglomeration and improves their wettability. Functionalization
may also give better adhesion to the matrix by introducing compatible functional groups on the carbon nanotube
surface.
It is observed that particle size and shape, mixing time on filler distribution, filler concentration, composite
processing technique, and filler/matrix interactions significantly affects the electrical resistance of expanded graphite
particle containing nanocomposites.

FUTURE CONSIDERATIONS
Prepared nylon 6 \ carbon nanotube nanocomposite will be examined critically with transmission electron
microscopy (TEM) for polymer-nanotube interaction and nanotube dispersion in polymer matrix.
Comparison in mechanical properties of prepared neat fibers and films and those of nanocomposites will be done
using Instron and nondestructive ultrasonic inspection system.
The electrical resistance of graphite embedded nanocomposites will be quantified and the significance of each
parameter e.g. particle size and shape, mixing time on filler distribution, filler concentration, composite processing
technique, and filler/matrix interactions will be examined.

REFERENCES
1. R. Saito, G. Dresselhaus, M. S. Dresselhaus, Physical Properties of Carbon Nanotubes, Imperial College Press,
London, U. K. (1998)
2. Thomas Tiano, Margaret Roylance, John Gassner, Functionalization Of Single-Wall Nanotubes For Improved
Structural Composites, Proceedings of 32nd International SAMPE Technical Conference, November 5-9, 2000,
Boston, MA
3. Hari Singh Nalwa; Handbook of Organic Conductive Molecules and Polymers, Volume 1, Charge-Transfer Slats,
Fullerenes and Photoconductors; John Wiley & Sons, 1997.
4. Xiao-Mei Chen, Jing-Wei Shen, Wen-Yi Huang; Novel electrically conductive polypropylene/graphite
nanocomposites; Journal of Materials Science Letters, 21, 2002,213-214.
5. Guo-Hua Chen, Da-Jun Wu, Wen-Gui Weng, Wen-Li Yan; Dispersion of Graphite Nanosheets in a Polymer
Matrix and the Conducting Property of the Nanocomposites; Polymer Engineering and Science, Vol 41, No.12,
December 2001.
6. Wenge Zheng, Shing-Chung Wong, Hung-Jue Sue; Transport Behaviour of PMMA/expanded graphite
nanocomposites; Polymer, 73, 6767-6773, 2002.
7. Guo-Hua Chen, Preparation of polystyrene-graphite conducting nanocomposites via intercalation polymerization;
Polymer International, 50, 980-985, 2001.
Website: http://www.umassd.edu/engineering/textiles/research/nanocompositefibers_files/frame.htm

National Textile Center Annual Report: November 2003